WO1994024078A1 - Continuous production process of tertiary alcohols by radical addition of secondary alcohols to alkenes - Google Patents

Continuous production process of tertiary alcohols by radical addition of secondary alcohols to alkenes Download PDF

Info

Publication number
WO1994024078A1
WO1994024078A1 PCT/EP1994/001214 EP9401214W WO9424078A1 WO 1994024078 A1 WO1994024078 A1 WO 1994024078A1 EP 9401214 W EP9401214 W EP 9401214W WO 9424078 A1 WO9424078 A1 WO 9424078A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
alcohols
reaction mixture
carried out
alkenes
Prior art date
Application number
PCT/EP1994/001214
Other languages
German (de)
French (fr)
Inventor
Michael Gnann
Maria Eckert
Robert RIETH
Original Assignee
Peroxid-Chemie Gmbh
TOJEK-RIETH, Johanna
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Peroxid-Chemie Gmbh, TOJEK-RIETH, Johanna filed Critical Peroxid-Chemie Gmbh
Priority to US08/532,577 priority Critical patent/US5831134A/en
Priority to DE59407306T priority patent/DE59407306D1/en
Priority to JP6522774A priority patent/JPH08508982A/en
Priority to EP94914408A priority patent/EP0695284B1/en
Publication of WO1994024078A1 publication Critical patent/WO1994024078A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols

Definitions

  • the present invention relates to a new process for the preparation of tertiary alcohols by radical addition of secondary alcohols to carbon-carbon double bond systems.
  • US-A-3,352,929 describes the production of condensation products from isopropanol and acetylene compounds. This process can be carried out in two stages, the first stage comprising the reaction of an acetylene compound with isopropanol to form an alkenol, and the second stage comprising the addition of a further isopropanol to form a saturated tertiary (polyhydric) alcohol. This can tion Reak ⁇ in the presence of organic peroxides as Kataly ⁇ sator be performed.
  • a serious disadvantage of the reactions described above is that the high contact time of the reactants of several hours results in considerable proportions of tele or polymer by-products in the reaction mixture.
  • Another disadvantage of the prior art methods is the low space / time yield of monomeric addition product due to the long reaction time.
  • the object on which the present invention is based was therefore to provide a process for the preparation of tertiary alcohols by addition of secondary alcohols to alkenes, in which the above-mentioned disadvantages can be avoided completely or at least largely.
  • the object according to the invention is achieved by a process for the preparation of tertiary alcohols by radical addition of secondary alcohols to alkenes, which is characterized in that the reaction is carried out as a continuous process in the presence of an organic peroxide as radical initiator and with an average contact time of Reaction mixture carried out up to a maximum of 1 hour.
  • R 2 , R 3 and R 4 are hydrogen or optionally substituted alkyl or aryl radicals and R 5 and ⁇ are optionally substituted alkyl or aryl radicals.
  • alkenes preference is given to using compounds having 2 to 20 carbon atoms, particularly preferably 4 to 16 carbon atoms, which can optionally carry substituents which do not impair the reaction (for example OH groups, O-alkyl groups, aromatic groups).
  • substituents for example OH groups, O-alkyl groups, aromatic groups.
  • particularly preferred alkenes are 2-methyl-3-buten-2-ol, 3-methyl-3-buten-1-ol, 1-tetradecene, 1-dodecene, cyclohexene and ⁇ -methylstyrene.
  • the most preferred alkene is 2-methyl-3-buten-2-ol.
  • Substances with preferably 3 to 14 carbon atoms, particularly preferably 3 to 10 carbon atoms, are used as secondary alcohol in the process according to the invention. It is further preferred that the secondary alcohol is used in an excess of 3 to 50 mol, particularly preferably 3 to 20 mol, of alcohol per mol of alkene used.
  • Specific examples of preferred secondary alcohols are 2-propanol (isopropanol), 2-butanol, 2-octanol, cyclohexanol, 3,3-dimethylbutan-2-ol, 2,6-dimethylheptan-4-ol and 1-phenylethanol.
  • the most preferred secondary alcohol is isopropanol.
  • the process according to the invention is therefore particularly preferably used for the addition of isopropanol to 2-methyl-3-buten-2-ol, 2,5-dimethylhexane-2,5-diol being formed as the addition product.
  • the process according to the invention is also carried out in the presence of an organic peroxide as a free radical initiator.
  • organic peroxides are peroxycarboxylic acid esters (e.g. tert-butyl peroxypivalate, tert-amyl peroxypivalate), dialkyl peroxides (e.g. di-tert-butyl peroxide, di-tert-amyl peroxide) and peroxy ketals.
  • the amount of the radical initiator is preferably 1 to 50 mole percent, particularly preferably 5 to 30 mole percent, based on the alkene used.
  • the temperature in the process according to the invention is preferably between 50 and 240 ° C., particularly preferably between 80 and 200 ° C.
  • the temperature is preferably between 150 and 200 ° C.
  • the reaction can be carried out under normal pressure or under elevated pressure. However, it is generally preferred to carry out the reaction under elevated pressure and in a pressure tube reactor. In such a procedure, the pressure can be, for example, in a range from 5 to 100 bar (500 kPa to 10000 kPa).
  • Figure 1 shows a diagram for a particularly preferred embodiment of the method according to the invention.
  • the reactants namely the alkene (A), the radical initiator (B) and the secondary alcohol (C) are fed via three separate lines into a mixing vessel 10 which is provided with a stirrer 12.
  • the reaction mixture is passed from the mixing vessel 10 via a pump 14 into a tubular reactor 16 which is located in a heating bath 16a with a heating element 16b and stirrer 16c.
  • the contact time of the reaction mixture in the tubular reactor is preferably 10 to 20 minutes.
  • the mixture is then passed through a cooler 18 and a pressure relief valve 20 to a receptacle 22.
  • the reaction mixture is passed from the receptacle 22 to a distillation unit 24 which is equipped with a heating bath 24a. There, the reaction product (D) can be isolated from the distillation residue after the unreacted secondary alcohol (C) has been distilled off.
  • the secondary alcohol (C) distilled off is in a distillate vessel 26 collected and from there again added to the mixing vessel 10.
  • 2-Methyl-3-buten-2-ol, 2-propanol and di-tert-butyl peroxide are passed in a molar ratio of 1:10: 0.2 into a vessel provided with a stirrer and mixed there.
  • This reaction mixture is pumped continuously at a pressure of 3000 kPa through the coils of a 1000 ml tube reactor.
  • the tubular reactor is located in a heated bath heated to 180 ° C.
  • the flow rate through the tubular reactor is adjusted so that the contact time of the reaction mixture in the reactor is approximately 15 minutes (3.8 l / h).
  • the olefin used was completely converted during this time.
  • 1-Tetradecene, 2-propanol and di-tert-butyl peroxide are reacted in a molar ratio of 1:15: 0.1, as described in Example 1, at a pressure of 3000 kPa.
  • the contact time of the reaction mixture in the reactor heated to 175 ° C is about 20 minutes.
  • 1-Tetradecen has completely implemented after this time.
  • the addition product, 2-methyl-2-hexadecanol is formed with a selectivity of 65% and, as described in Example 1, isolated.
  • 2-methyl-3-buten-2-ol, cyclohexanol and di-tert-butyl peroxide are used at 180 ° C. in a molar ratio of 1:15: 0.25 at a pressure of 2500 kPa, as described in Example 1 Brought reaction. After a reaction time of 15 minutes, the 2-methyl-3-buten-2-ol used has completely reacted.
  • the addition product, as described in Example 1, is isolated from the distillation residue with a selectivity of 85%.
  • 2-methyl-3-buten-2-ol, 2-propanol and tert-butyl peroxy pivalate (75% solution in aliphatic) are in a molar ratio of 1:15: 0.3 at 90 ° C. and a Pressure of 500 kPa, as described in Example 1, brought to reaction. After 20 minutes of contact time of the reaction mixture in the tubular reactor, 95% of the olefin used had reacted. 2,5-dimethylhexane-2,5-diol is formed with 76% selectivity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process is disclosed for producing tertiary alcohols by radical addition of secondary alcohols to alkenes. The reaction is carried out as a continuous process in the presence of an organic peroxide as radical initiator and during a mean contact time of the reaction mixture of up to maximum 1 hour.

Description

KONTINUIERLICHER PROZESS ZUR HERSTELLUNG VON TERTIÄREN ALKOHOLEN DURCH RADIKALISCHE ADDITIONSREAKTION VON SEKUNDÄREN ALKOHOLEN AN ALKENE CONTINUOUS PROCESS FOR THE PRODUCTION OF TERTIARY ALCOHOLS BY RADICAL ADDITIONAL REACTION FROM SECONDARY ALCOHOLS TO ALKENES
BESCHREIBUNGDESCRIPTION
Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von tertiären Alkoholen durch radikalische Addi¬ tion von sekundären Alkoholen an Kohlenstoff-Kohlenstoff- DoppelbindungsSysteme.The present invention relates to a new process for the preparation of tertiary alcohols by radical addition of secondary alcohols to carbon-carbon double bond systems.
Die Addition von sekundären Alkoholen an Alkene unter Bildung von tertiären Alkoholen ist prinzipiell in der Technik be¬ kannt.The addition of secondary alcohols to alkenes to form tertiary alcohols is known in principle in the art.
US-A-3,352,929 beschreibt die Herstellung von Kondensations¬ produkten aus Isopropanol und Acetylenverbindungen. Dieses Verfahren kann in zwei Stufen durchgeführt werden, wobei die erste Stufe die Reaktion einer Aσetylenverbindung mit Isopro¬ panol zu einem Alkenol umfaßt, und die zweite Stufe die Addi¬ tion eines weiteren Isopropanols unter Bildung eines gesät¬ tigten tertiären (mehrwertigen) Alkohols umfaßt. Diese Reak¬ tion kann in Gegenwart von organischen Peroxiden als Kataly¬ sator durchgeführt werden. Gemäß US-A-3,352,929 (Spalte 5, Zeilen 43-51) ist für die erste Stufe der Reaktion, nämlich die Addition eines sekundären Alkohols an eine Kohlenstoff- Kohlenstoff-Dreifachbindung, nur eine geringe Reaktionsdauer von z.B. 5 Minuten erforderlich, während für die zweite Stu¬ fe, nämlich die Addition eines weiteren Moleküls Isopropanol an das eine Kohlenstoff-Kohlenstoff-Doppelbindung aufweisende Additionεprodukt der ersten Reaktionsstufe, eine erheblich längere Reaktionsdauer von etwa 2 bis 5 Stunden erforderlich ist.US-A-3,352,929 describes the production of condensation products from isopropanol and acetylene compounds. This process can be carried out in two stages, the first stage comprising the reaction of an acetylene compound with isopropanol to form an alkenol, and the second stage comprising the addition of a further isopropanol to form a saturated tertiary (polyhydric) alcohol. This can tion Reak¬ in the presence of organic peroxides as Kataly ¬ sator be performed. According to US-A-3,352,929 (column 5, lines 43-51) for the first stage of the reaction, namely the addition of a secondary alcohol to a carbon-carbon triple bond, only a short reaction time of, for example, 5 minutes is required, while for the second stage, namely the addition of another molecule of isopropanol to the carbon-carbon double bond addition product of the first reaction stage, a considerably longer reaction time of about 2 to 5 hours is required.
Weiterhin ist aus Methoden der organischen Chemie (Houben- Weyl), Band VI/lb, Georg Thieme Verlag Stuttgart, New York, 1984, Seite 654 ff) bekannt, daß durch Addition von Alkoholen (z.B. sekundären Alkoholen wie etwa Isopropanol, Isobutanol) an Alkene tertiäre Alkohole erhalten werden können. Die Reaktion erfolgt durch Erhitzen des Olefins in überschüssigem Alkohol (in einem Molverhältnis von Olefin zu Alkohol von 1:10-50) unter Zusatz eines Dialkylperoxidε als Initiator (10 bis 20 Molprozent bezüglich des Olefins) auf 110 bis 135°C für eine Zeitdauer von 35 bis 40 Stunden. In dieser Litera¬ turstelle ist beschrieben, daß bei dieser Reaktion durch Telomerisation überwiegend höhere Alkohole erhalten werden, während das monomere Additionsprodukt nur in einer relativ geringen Ausbeute entsteht.Furthermore, from methods of organic chemistry (Houben-Weyl), Volume VI / lb, Georg Thieme Verlag Stuttgart, New York, 1984, page 654 ff) it is known that by adding alcohols (eg secondary alcohols such as isopropanol, isobutanol) tertiary alcohols can be obtained on alkenes. The reaction is carried out by heating the olefin in excess alcohol (in a molar ratio of olefin to alcohol of 1: 10-50) with the addition of a dialkyl peroxide as initiator (10 to 20 mol percent with respect to the olefin) to 110 to 135 ° C. for a period of 35 to 40 hours. In this literature it is described that predominantly higher alcohols are obtained in this reaction by telomerization, while the monomeric addition product is formed only in a relatively low yield.
Ein schwerwiegender Nachteil der oben beschriebenen Reaktio¬ nen besteht somit darin, daß durch die hohe Kontaktzeit der Reaktanden von mehreren Stunden erhebliche Anteile an telo e- ren bzw. polymeren Nebenprodukten im Reaktionsgemisch entste¬ hen. Ein weiterer Nachteil der Verfahren des Standes der Technik ist die durch die lange Reaktionsdauer bedingte ge¬ ringe Raum/Zeit-Ausbeute an monomerem Additionsprodukt.A serious disadvantage of the reactions described above is that the high contact time of the reactants of several hours results in considerable proportions of tele or polymer by-products in the reaction mixture. Another disadvantage of the prior art methods is the low space / time yield of monomeric addition product due to the long reaction time.
Die der vorliegenden Erfindung zugrundeliegende Aufgabe be¬ stand somit darin, ein Verfahren zur Herstellung von tertiä¬ ren Alkoholen durch Addition von sekundären Alkoholen an Alkene bereitzustellen, bei dem die oben genannten Nachteile völlig oder zumindest weitgehend vermieden werden können.The object on which the present invention is based was therefore to provide a process for the preparation of tertiary alcohols by addition of secondary alcohols to alkenes, in which the above-mentioned disadvantages can be avoided completely or at least largely.
Die erfindüngsgemäße Aufgabe wird gelöst durch ein Verfahren zur Herstellung von tertiären Alkoholen durch radikalische Addition von sekundären Alkoholen an Alkene, welches dadurch gekennzeichnet ist, daß man die Reaktion als koninuierlichen Prozeß in Gegenwart eines organischen Peroxids als radikali¬ schem Initiator und mit einer mittleren Kontaktzeit des Reak¬ tionsgemisches von bis zu maximal 1 Stunde durchführt.The object according to the invention is achieved by a process for the preparation of tertiary alcohols by radical addition of secondary alcohols to alkenes, which is characterized in that the reaction is carried out as a continuous process in the presence of an organic peroxide as radical initiator and with an average contact time of Reaction mixture carried out up to a maximum of 1 hour.
Überraschenderweise wurde festgestellt, daß durch die konti¬ nuierliche Verfahrensführung gemäß vorliegender Erfindung bereits bei einer Kontaktzeit des Reaktionsgemisches von bis zu maximal 1 Stunde, vorzugsweise bis zu maximal 30 Minuten, besonders bevorzugt bis zu maximal 20 Minuten ein monomeres Additionsprodukt in hoher Raum/Zeit-Ausbeute und mit einem geringeren Anteil an poly eren oder/und telomeren Nebenpro¬ dukten erhalten wird.Surprisingly, it was found that the continuous procedure according to the present invention Already with a contact time of the reaction mixture of up to a maximum of 1 hour, preferably up to a maximum of 30 minutes, particularly preferably up to a maximum of 20 minutes, a monomeric addition product in a high space / time yield and with a lower proportion of polymeric and / or telomeric secondary pro ¬ products is obtained.
Die Herstellung von tertiären Alkoholen durch eine radikali¬ sche Additionsreaktion von sekundären Alkoholen an Kohlen¬ stoff-Kohlenstoff-Doppelbindungssysteme findet nach dem folgenden ReaktionsSchema statt:The production of tertiary alcohols by a radical addition reaction of secondary alcohols on carbon-carbon double bond systems takes place according to the following reaction scheme:
Figure imgf000005_0001
Figure imgf000005_0001
wobei B.- , R2 , R3 und R4 Wasserstoff oder gegebenenfalls sub¬ stituierte Alkyl- oder Arylreste bedeuten und R5 und ^ gege¬ benenfalls substituierte Alkyl- oder Arylreste bedeuten.where B.-, R 2 , R 3 and R 4 are hydrogen or optionally substituted alkyl or aryl radicals and R 5 and ^ are optionally substituted alkyl or aryl radicals.
Das erfindungsgemäße Verfahren besitzt einen breiten Anwen¬ dungsbereich, da es vorteilhaft mit einer großen Zahl ver¬ schiedener Alkene und sekundärer Alkohole durchgeführt werden kann. Als Alkene verwendet man vorzugsweise Verbindungen mit 2 bis 20 C-Atomen, besonders bevorzugt 4 bis 16 C-Atomen, die gegebenenfalls Substituenten tragen können, welche die Reak¬ tion nicht beeinträchtigen (z.B. OH-Gruppen, O-Alkylgruppen, aromatische Gruppen). Spezifische Beispiele für besonders bevorzugte Alkene sind 2-Methyl-3-buten-2-ol, 3-Methyl-3- buten-1-ol, 1-Tetradecen, 1-Dodecen, Cyclohexen und α-Methyl- styrol. Das am meisten bevorzugte Alken ist 2-Methyl-3-buten- 2-ol.The process according to the invention has a wide range of applications since it can advantageously be carried out with a large number of different alkenes and secondary alcohols. As alkenes, preference is given to using compounds having 2 to 20 carbon atoms, particularly preferably 4 to 16 carbon atoms, which can optionally carry substituents which do not impair the reaction (for example OH groups, O-alkyl groups, aromatic groups). Specific examples of particularly preferred alkenes are 2-methyl-3-buten-2-ol, 3-methyl-3-buten-1-ol, 1-tetradecene, 1-dodecene, cyclohexene and α-methylstyrene. The most preferred alkene is 2-methyl-3-buten-2-ol.
Als sekundärer Alkohol werden bei dem erfindungsgemäßen Ver¬ fahren Substanzen mit vorzugsweise 3 bis 14 C-Atomen, beson¬ ders bevorzugt 3 bis 10 C-Atomen verwendet. Weiterhin ist es bevorzugt, daß der sekundäre Alkohol in einem Überschuß von 3 bis 50 Mol, besonders bevorzugt von 3 bis 20 Mol Alkohol pro Mol eingesetztem Alken verwendet wird. Spezifische Beispiele für bevorzugte sekundäre Alkohole sind 2-Propanol (Isopropa¬ nol), 2-Butanol, 2-Octanol, Cyclohexanol, 3,3-Dimethylbutan- 2-ol, 2,6-Dimethylheptan-4-ol und 1-Phenylethanol. Der am meisten bevorzugte sekundäre Alkohol ist Isopropanol.Substances with preferably 3 to 14 carbon atoms, particularly preferably 3 to 10 carbon atoms, are used as secondary alcohol in the process according to the invention. It is further preferred that the secondary alcohol is used in an excess of 3 to 50 mol, particularly preferably 3 to 20 mol, of alcohol per mol of alkene used. Specific examples of preferred secondary alcohols are 2-propanol (isopropanol), 2-butanol, 2-octanol, cyclohexanol, 3,3-dimethylbutan-2-ol, 2,6-dimethylheptan-4-ol and 1-phenylethanol. The most preferred secondary alcohol is isopropanol.
Besonders bevorzugt wird das erfindungsgemäße Verfahren daher zur Addition von Isopropanol an 2-Methyl-3-buten-2-ol verwen¬ det, wobei als Additionsprodukt 2,5-Dimethylhexan-2,5-diol entsteht.The process according to the invention is therefore particularly preferably used for the addition of isopropanol to 2-methyl-3-buten-2-ol, 2,5-dimethylhexane-2,5-diol being formed as the addition product.
Das erfindungsgemäße Verfahren wird weiterhin in Gegenwart eines organischen Peroxids als radikalischem Initiator durch¬ geführt. Bevorzugte Beispiele für organische Peroxide sind Peroxycarbonsäureester (z.B. tert.-Butylperoxypivalat, tert.- Amylperoxypivalat) , Dialkylperoxide (z.B. Di-tert.-Butyl- peroxid, Di-tert.-Amylperoxid) und Peroxyketale. Die Menge des radikalischen Initiators beträgt vorzugsweise 1 bis 50 Molprozent, besonders bevorzugt 5 bis 30 Molprozent bezüglich des eingesetzten Alkens.The process according to the invention is also carried out in the presence of an organic peroxide as a free radical initiator. Preferred examples of organic peroxides are peroxycarboxylic acid esters (e.g. tert-butyl peroxypivalate, tert-amyl peroxypivalate), dialkyl peroxides (e.g. di-tert-butyl peroxide, di-tert-amyl peroxide) and peroxy ketals. The amount of the radical initiator is preferably 1 to 50 mole percent, particularly preferably 5 to 30 mole percent, based on the alkene used.
Die Temperatur bei dem erfindungsgemäßen Verfahren beträgt vorzugsweise je nach eingesetztem radikalischen Initiator zwischen 50 und 240°C, besonders bevorzugt zwischen 80 und 200°C. Bei Verwendung von Di-tert.-Butylperoxid als Initiator beträgt die Temperatur vorzugsweise zwischen 150 und 200°C. Je nach eingesetztem Alken kann die Reaktion unter Normal¬ druck oder unter erhöhtem Druck durchgeführt werden. Es ist jedoch im allgemeinen bevorzugt, die Reaktion unter erhöhtem Druck und in einem Druck-Rohrreaktor durchzuführen. Bei einer derartigen Verfahrensführung kann der Druck beispielsweise in einem Bereich von 5 bis 100 bar (500 kPa bis 10000 kPa) lie¬ gen.Depending on the radical initiator used, the temperature in the process according to the invention is preferably between 50 and 240 ° C., particularly preferably between 80 and 200 ° C. When using di-tert-butyl peroxide as an initiator, the temperature is preferably between 150 and 200 ° C. Depending on the alkene used, the reaction can be carried out under normal pressure or under elevated pressure. However, it is generally preferred to carry out the reaction under elevated pressure and in a pressure tube reactor. In such a procedure, the pressure can be, for example, in a range from 5 to 100 bar (500 kPa to 10000 kPa).
Weiterhin ist es bei dem erfindungsgemäßen Verfahren bevor¬ zugt, nach Beendigung der Reaktion überschüssigen sekundären Alkohol aus dem Produktgemisch kontinuierlich zu entfernen (z.B. durch Destillation) und in das Reaktionsge iεch zurück¬ zuführen.Furthermore, it is preferred in the process according to the invention to remove excess secondary alcohol from the product mixture continuously (e.g. by distillation) after the reaction has ended and to return it to the reaction mixture.
In Abbildung 1 ist ein Diagramm für eine besonders bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens zu erkennen. Dabei werden die Reaktionspartner, nämlich das Alken (A) , der radikalische Initiator (B) und der sekundäre Alkohol (C) über drei getrennte Leitungen in ein Miεchgefäß 10 geleitet, das mit einem Rührer 12 versehen ist. Das Reaktionsgemiεch wird aus dem Mischgefäß 10 über eine Pumpe 14 in einen Rohrreaktor 16 geleitet, der sich in einem Heizbad 16a mit Heizstab 16b und Rührer 16c befindet. Die Kontaktzeit des Reaktionsgemi¬ sches im Rohrreaktor beträgt dabei vorzugsweise 10 bis 20 Minuten. Dann wird das Gemisch durch einen Kühler 18 und ein Druckentspannungsventil 20 zu einem Aufnahmegefäß 22 gelei¬ tet. Vom Aufnahmegefäß 22 wird das Reaktionsgemisch zu einer Destillationseinheit 24 geleitet, die mit einem Heizbad 24a ausgestattet ist. Dort kann das Reaktionsprodukt (D) nach dem Abdestillieren von nicht umgesetztem sekundärem Alkohol (C) aus dem Destillationsrückstand isoliert werden. Der abdestil¬ lierte sekundäre Alkohol (C) wird in einem Destillatgefäß 26 gesammelt und von dort aus wieder dem Mischgefäß 10 zudo¬ siert.Figure 1 shows a diagram for a particularly preferred embodiment of the method according to the invention. The reactants, namely the alkene (A), the radical initiator (B) and the secondary alcohol (C) are fed via three separate lines into a mixing vessel 10 which is provided with a stirrer 12. The reaction mixture is passed from the mixing vessel 10 via a pump 14 into a tubular reactor 16 which is located in a heating bath 16a with a heating element 16b and stirrer 16c. The contact time of the reaction mixture in the tubular reactor is preferably 10 to 20 minutes. The mixture is then passed through a cooler 18 and a pressure relief valve 20 to a receptacle 22. The reaction mixture is passed from the receptacle 22 to a distillation unit 24 which is equipped with a heating bath 24a. There, the reaction product (D) can be isolated from the distillation residue after the unreacted secondary alcohol (C) has been distilled off. The secondary alcohol (C) distilled off is in a distillate vessel 26 collected and from there again added to the mixing vessel 10.
Die Erfindung wird weiterhin durch die folgenden Beispiele veranschaulicht.The invention is further illustrated by the following examples.
BEISPIEL 1EXAMPLE 1
2-Methyl-3-buten-2-ol, 2-Propanol und Di-tert.-butylperoxid werden in einem Molverhältnis von 1:10:0,2 in ein mit einem Rührer versehenes Gefäß geleitet und dort vermischt. Dieses Reaktionεgemisch wird bei einem Druck von 3000 kPa konti¬ nuierlich durch die Rohrschlangen eines 1000 ml Rohrreaktorε gepumpt. Dabei befindet sich der Rohrreaktor in einem auf 180°C geheizten Wäπnebad. Die Durchflußrate durch den Rohr¬ reaktor wird so eingestellt, daß die Kontaktzeit des Reak- tionsgemischeε im Reaktor ca. 15 Minuten beträgt (3,8 1/h). Das eingesetzte Olefin hat sich in dieεer Zeit vollεtändig umgesetzt.2-Methyl-3-buten-2-ol, 2-propanol and di-tert-butyl peroxide are passed in a molar ratio of 1:10: 0.2 into a vessel provided with a stirrer and mixed there. This reaction mixture is pumped continuously at a pressure of 3000 kPa through the coils of a 1000 ml tube reactor. The tubular reactor is located in a heated bath heated to 180 ° C. The flow rate through the tubular reactor is adjusted so that the contact time of the reaction mixture in the reactor is approximately 15 minutes (3.8 l / h). The olefin used was completely converted during this time.
Nach Verlasεen des Reaktors wird das Reaktionsgemisch abge¬ kühlt und über ein Druckreduzierventil in einem Aufnahmebe¬ hälter gesammelt, von dem es in eine Destillationsvorrichtung geleitet werden kann. Bei der anschließenden Destillation wird das überschüssige 2-Propanol entfernt und kontinuierlich in den Prozeß rückgeführt. Das Additionsprodukt 2,5-Dimethyl- hexan-2,5-diol befindet sich im Deεtillationsrückstand. Es werden 380 g Produkt/h gewonnen (Reinheit > 97 GC-Fl.-%). BEISPIEL 2After leaving the reactor, the reaction mixture is cooled and collected via a pressure reducing valve in a receptacle, from which it can be passed into a distillation device. In the subsequent distillation, the excess 2-propanol is removed and continuously returned to the process. The addition product 2,5-dimethyl-hexane-2,5-diol is in the distillation residue. 380 g of product / h are obtained (purity> 97 GC area%). EXAMPLE 2
1-Tetradecen, 2-Propanol und Di-tert.-butylperoxid werden in einem Molverhältnis von 1 : 15 : 0,1, wie in Beispiel 1 be¬ schrieben, bei einem Druck von 3000 kPa zur Reaktion ge¬ bracht. Die Kontaktzeit des Reaktionsgemisches im auf 175°C beheizten Reaktor beträgt ca. 20 Minuten. 1-Tetradecen hat sich nach dieser Zeit vollständig umgesetzt. Das Additionε- produkt, 2-Methyl-2-hexadecanol, wird mit einer Selektivität von 65 % gebildet und, wie in Beispiel 1 beschrieben, iso¬ liert.1-Tetradecene, 2-propanol and di-tert-butyl peroxide are reacted in a molar ratio of 1:15: 0.1, as described in Example 1, at a pressure of 3000 kPa. The contact time of the reaction mixture in the reactor heated to 175 ° C is about 20 minutes. 1-Tetradecen has completely implemented after this time. The addition product, 2-methyl-2-hexadecanol, is formed with a selectivity of 65% and, as described in Example 1, isolated.
BEISPIEL 3EXAMPLE 3
2-Methyl-3-buten-2-ol, Cyclohexanol und Di-tert.-butylperoxid werden bei 180°C in einem Molverhältnis von 1 : 15 : 0,25 bei einem Druck von 2500 kPa, wie in Beispiel 1 beschrieben, zur Reaktion gebracht. Nach einer Reaktionszeit von 15 Minuten hat sich das eingesetzte 2-Methyl-3-buten-2-ol bereitε voll- εtändig umgesetzt. Aus dem Destillationsrückstand wird das Additionsprodukt, wie in Beispiel 1 beschrieben, mit einer Selektivität von 85 % isoliert.2-methyl-3-buten-2-ol, cyclohexanol and di-tert-butyl peroxide are used at 180 ° C. in a molar ratio of 1:15: 0.25 at a pressure of 2500 kPa, as described in Example 1 Brought reaction. After a reaction time of 15 minutes, the 2-methyl-3-buten-2-ol used has completely reacted. The addition product, as described in Example 1, is isolated from the distillation residue with a selectivity of 85%.
BEISPIEL 4EXAMPLE 4
2-Methyl-3-buten-2-ol, 2-Propanol und tert.-Butylperoxy- pivalat (75 %ige Lösung in Aliphaten) werden in einem Molver¬ hältnis von 1 : 15 : 0,3 bei 90°C und einem Druck von 500 kPa, wie in Beispiel 1 beεchrieben, zur Reaktion gebracht. Nach 20 Minuten Kontaktzeit des Reaktionsgemischeε im Rohr-- reaktor hat sich das eingesetzte Olefin zu 95 % umgesetzt. 2,5-Dimethylhexan-2,5-diol wird mit 76 % Selektivität gebil¬ det. 2-methyl-3-buten-2-ol, 2-propanol and tert-butyl peroxy pivalate (75% solution in aliphatic) are in a molar ratio of 1:15: 0.3 at 90 ° C. and a Pressure of 500 kPa, as described in Example 1, brought to reaction. After 20 minutes of contact time of the reaction mixture in the tubular reactor, 95% of the olefin used had reacted. 2,5-dimethylhexane-2,5-diol is formed with 76% selectivity.

Claims

PATENTANSPRÜCHE PATENT CLAIMS
1. Verfahren zur Herstellung von tertiären Alkoholen durch radikalische Addition von sekundären Alkoholen an Alke¬ ne, d a d u r c h g e k e n n z e i c h n e t , daß man die Reaktion als kontinuierlichen Prozeß in Gegenwart eines organischen Peroxids als radikalischem Initiator und mit einer mittleren Kontaktzeit des Reak- tionsgemischeε von biε zu maximal 1 Stunde durchführt.1. A process for the preparation of tertiary alcohols by radical addition of secondary alcohols to Alke¬ ne, characterized in that the reaction as a continuous process in the presence of an organic peroxide as a radical initiator and with an average contact time of the reaction mixture from biε to a maximum of 1 Hour.
2. Verfahren nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t , daß man die Reaktion mit einer mittleren Kontaktzeit des Reaktionsgemiεcheε von bis zu maximal 30 Minuten durch¬ führt .2. The method according to claim 1, which also means that the reaction is carried out with an average contact time of the reaction mixture of up to a maximum of 30 minutes.
3. Verfahren nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t , daß man ein Alken mit 2 biε 20 C-Atomen verwendet.3. The method according to claim 1 or 2, d a d u r c h g e k e n n z e i c h n e t that one uses an alkene with 2 bis 20 C-atoms.
4. Verfahren nach einem der Ansprüche 1 bis 3, d a d u r c h g e k e n n z e i c h n e t , daß man einen sekundären Alkohol mit 3 bis 14 C-Atomen verwendet.4. The method according to any one of claims 1 to 3, d a d u r c h g e k e n n z e i c h n e t that a secondary alcohol having 3 to 14 carbon atoms is used.
5. Verfahren nach einem der Ansprüche 1 bis 4, d a d u r c h g e k e n n z e i c h n e t , daß man den sekundären Alkohol in einem Verhältnis von 3 bis 50 Mol pro Mol des eingesetzten Alkens verwendet.5. The method according to any one of claims 1 to 4, that the secondary alcohol is used in a ratio of 3 to 50 moles per mole of the alkene used.
6. Verfahren nach einem der Ansprüche 1 bis 5, d a d u r c h g e k e n n z e i c h n e t , daß man als radikalischen Initiator Peroxycarbonsäure- ester oder Dialkylperoxide verwendet. 6. The method according to any one of claims 1 to 5, characterized in that peroxycarboxylic acid ester or dialkyl peroxides are used as the radical initiator.
7. Verfahren nach einem der Ansprüche 1 bis 6, d a d u r c h g e k e n n z e i c h n e t , daß man den Initiator in einem Verhältnis von 1 bis 50 Molprozent bezüglich des eingesetzten Alkens verwendet.7. The method according to any one of claims 1 to 6, that the initiator is used in a ratio of 1 to 50 mol percent with respect to the alkene used.
8. Verfahren nach einem der Anεprüche 1 biε 7, d a d u r c h g e k e n n z e i c h n e t , daß man die Reaktion bei einer Temperatur von 50 biε 240°C und unter Normaldruck oder erhöhtem Druck durch¬ führt.8. The method according to any one of claims 1 to 7, that means that the reaction is carried out at a temperature of from 50 to 240 ° C. and under normal pressure or elevated pressure.
9. Verfahren nach einem der Anεprüche 1 bis 8, d a d u r c h g e k e n n z e i c h n e t , daß man die Reaktion in einem Rohrreaktor unter erhöhtem Druck durchführt.9. The method according to any one of claims 1 to 8, that the reaction is carried out in a tubular reactor under elevated pressure.
10. Verfahren nach einem der vorhergehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t , daß man nach Durchführung der Reaktion das Produkt aus dem Reaktionsgemisch abtrennt und nicht umgeεetzten sekundären Alkohol in das Reaktionsgemiεch rückführt. 10. The method according to any one of the preceding claims, that the product is separated from the reaction mixture after the reaction has been carried out and the unreacted secondary alcohol is recycled into the reaction mixture.
PCT/EP1994/001214 1993-04-20 1994-04-19 Continuous production process of tertiary alcohols by radical addition of secondary alcohols to alkenes WO1994024078A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US08/532,577 US5831134A (en) 1993-04-20 1994-04-19 Continuous production process of tertiary alcohols by radical addition of secondary alcohols to alkenes
DE59407306T DE59407306D1 (en) 1993-04-20 1994-04-19 CONTINUOUS PROCESS FOR THE PRODUCTION OF TERTIARY ALCOHOLS BY RADICAL ADDITIONAL REACTION OF SECONDARY ALCOHOLS TO ALKENES
JP6522774A JPH08508982A (en) 1993-04-20 1994-04-19 Continuous production of tertiary alcohols by radical addition of secondary alcohols to alkenes.
EP94914408A EP0695284B1 (en) 1993-04-20 1994-04-19 Continuous production process of tertiary alcohols by radical addition of secondary alcohols to alkenes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4312815A DE4312815A1 (en) 1993-04-20 1993-04-20 Production of tertiary alcohols by radical addition reaction of secondary alcohols to alkenes
DEP4312815.7 1993-04-20

Publications (1)

Publication Number Publication Date
WO1994024078A1 true WO1994024078A1 (en) 1994-10-27

Family

ID=6485876

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/001214 WO1994024078A1 (en) 1993-04-20 1994-04-19 Continuous production process of tertiary alcohols by radical addition of secondary alcohols to alkenes

Country Status (5)

Country Link
US (1) US5831134A (en)
EP (1) EP0695284B1 (en)
JP (1) JPH08508982A (en)
DE (2) DE4312815A1 (en)
WO (1) WO1994024078A1 (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2715306B1 (en) * 1994-01-25 1996-03-15 Oreal Cosmetic or dermopharmaceutical composition in the form of a flexible paste and process for the preparation of said composition.
US9488994B2 (en) * 2012-03-29 2016-11-08 Honeywell International Inc. Method and system for configuring wireless sensors in an HVAC system
MX2015013672A (en) 2013-03-28 2016-02-16 Procter & Gamble Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose.
JP6275864B2 (en) 2014-03-27 2018-02-07 ザ プロクター アンド ギャンブル カンパニー Cleaning composition containing polyetheramine
EP3122850A1 (en) 2014-03-27 2017-02-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015187757A1 (en) 2014-06-06 2015-12-10 The Procter & Gamble Company Detergent composition comprising polyalkyleneimine polymers
WO2016032992A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
US9951297B2 (en) 2014-08-27 2018-04-24 The Procter & Gamble Company Detergent composition compromising a cationic polymer containing a vinyl formamide nonionic structural unit
EP3186348B1 (en) 2014-08-27 2022-08-03 The Procter & Gamble Company Method of treating a fabric
WO2016032991A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
CA2959431C (en) 2014-09-25 2019-10-22 The Procter & Gamble Company Fabric care compositions containing a polyetheramine
KR20210071016A (en) * 2018-10-02 2021-06-15 시므라이즈 아게 Process for preparing alkanediols
CA3228918A1 (en) 2021-08-10 2023-02-16 Nippon Shokubai Co., Ltd. Polyalkylene-oxide-containing compound

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB708254A (en) * 1949-12-02 1954-05-05 Standard Oil Dev Co Improvements in or relating to the preparation of higher molecular weight alcohols and of olefins and detergent products therefrom
US3255260A (en) * 1962-01-04 1966-06-07 Chevron Res Product peaking by use of aqueous alcohol in telomerization

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB708254A (en) * 1949-12-02 1954-05-05 Standard Oil Dev Co Improvements in or relating to the preparation of higher molecular weight alcohols and of olefins and detergent products therefrom
US3255260A (en) * 1962-01-04 1966-06-07 Chevron Res Product peaking by use of aqueous alcohol in telomerization

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"METHODEN DER ORGANISCHEN CHEMIE TEIL3, BAND 6/1B", 1984, G. THIEME VERLAG, STUTTGART,DE *

Also Published As

Publication number Publication date
US5831134A (en) 1998-11-03
DE59407306D1 (en) 1998-12-24
DE4312815A1 (en) 1994-10-27
EP0695284B1 (en) 1998-11-18
JPH08508982A (en) 1996-09-24
EP0695284A1 (en) 1996-02-07

Similar Documents

Publication Publication Date Title
DE851496C (en) Process for the preparation of symmetrical or asymmetrical aliphatic, di-tertiary peroxides
EP0695284B1 (en) Continuous production process of tertiary alcohols by radical addition of secondary alcohols to alkenes
EP0317909B1 (en) Process for the preparation of alpha-alkyl acroleins
EP0008096B1 (en) Process for the synthesis of 2-(perfluoroalkyl)-ethanols
WO1991013918A1 (en) Method for producing polymerized alcohols
EP0005471B1 (en) Process for the preparation of 2,2,4-trimethyl-3-hydroxypentyl-isobutyrate
EP0026278B1 (en) Process for the preparation of tertiary phosphines
DE2937831C2 (en)
DE60104789T2 (en) Process for the preparation of 2,4,5-trialkylbenzaldehydes
DE3016571A1 (en) Per-fluoroalkyl-alkanol prepn. by hydrolysis of iodo-alkane - in presence of metal cation, phase-transfer catalyst and/or per-fluoroalkyl carboxylic acid anion
DE2052782B2 (en) Process for the preparation of olefinically unsaturated compounds by dehydrating alcohols
DE852851C (en) Process for the preparation of alkyl esters ª ‡, ª ‰ -unsaturated monocarboxylic acids
DE1668848A1 (en) Process for the production of aetherperoxides from alpha-substituted vinyl ethers and new aetherperoxides
EP0352641B1 (en) Method for the production of alkyl esters of pentenoic acid
EP0829466B1 (en) Process for the preparation of cyclopentanols
CH630053A5 (en) METHOD FOR PRODUCING A MIXTURE FROM M-ARYLOXYBENZYL CHLORIDE AND M-ARYLOXYBENZALCHLORIDE.
EP0929505A1 (en) Process for preparing alkyne diols or mixtures of alkyne diols with alkyne monools
DE2430287A1 (en) PROCESS FOR MANUFACTURING UNSATATULATED ALCOHOLS
DE1768642A1 (en) Process for the preparation of optionally substituted 1-perfluoroalkyl-2-iodaethanes and 1-perfluoroalkyl-2-iodaethenes
DE4026712A1 (en) METHOD FOR PRODUCING TERTIARY FLUORINE ALCOHOLS
DE19706384C1 (en) Process for the preparation of diethyl ethanephosphonate
DE2439198C2 (en) 2,6,10-trimethyl-dodecan-1-al and 2,6,10-trimethyl-dodeca-4,8-dien-1-al and processes for their preparation
DE2042050C (en) Process for the production of 1-menthyl methyl carbonate or 1-menthyl ethyl carbonate
DE4445825A1 (en) Branched-chain mono:alkyl-phosphine(s) useful as flame retardant and antistatic for fibres and plastics
DE3033655C2 (en)

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): BR JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1994914408

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1994914408

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 08532577

Country of ref document: US

WWG Wipo information: grant in national office

Ref document number: 1994914408

Country of ref document: EP